Polyazodyestuffs



"' EUGEN GLIETENBERG, OF LEVERKUSEN-I. G.

ANILINE WORKS, INC, NEW YORK,

Patented Mar. 14, 1933 UNITED STATES PATE NT OFFICE, I;

-WERK, GERMANY, ASSIG-NOR 'I'O GENERAL N. Y., A CORPORATION OF DELAWARE,

'POLYAZODYESTUFFS No Drawing. Application filed .Tune 5, 1931, Serial No. 542,466, and in Germany June 1 0, 1930.

The present invention relates to new polyazodyestuffs, more particularly it relates to azodyestufi's which may be represented by the probable general formula:

koxy, B, may be substituted by a sulfonic acid group, alk stands for an alkyl group, ac

stands for an acyl .group,;such as an acetyl or benzoyl group, and it stands for one of the numbersone and two.

My new dyestuffs are obtainable by diazotizing an amino azo dyestuff of the general formula:

V wherein R R and R mean the same as stated above, coupling in an acid medium with an 1.2-aminonaphthol-alkyl-ether or a sulfonic acid thereof, again diazotizing and coupling in an alkaline medium with a peri acylamino-naphthol-sulfonic acid.

By the term yellow components I mean acid arylamides and substitution products thereof, methylketol and substitution prod-i ucts thereof and pyrazolones.

-Aminoazo compounds ofthe type of the second formula referred to above are for ,OOM

SOaH

| {lo s ng manner from sulfur and sulfur phenol, salicyllc acid or its derivatives capable of undergoing coupling, aceto-acetic They are obtainable by condensing the a1ninonitroaroylhalogenides alkali metal salts dark vegetable fibre to light.

powders, dyeing the green shades of good-fastness The invention is illustrated by the followmg examples, without being limited thereto:

Example 1 257 grams of the azodyestufi' p-phenylenediamine-azo-salicylic acid are dissolved in water until neutral and, afterthe. addition of 106 grams of sodium carbonate at -60 C., there are slowly added 200 grams of p-nitrobenzoylchloride.

When the condensation is complete, there action 120 The of about 5060 (l, and the aminoazocompound thus obtained is freed in the usual compounds.

The neutral solution of this monoazodyestuff is, after the addition of grams of sodium nitrite, run into 280 grams of cold hydrochloric acid (30%) the yellowish: brown diazoazo compound sucked off and coupled in an acid medium with 1 mol of 1.2-aminonaphthol-ethyl-ether- 6-sulfonic1acid. The coupling is complete after several hours, and by heating for 1 to 2 hours at 70-809 Cl, theamino-disazodyestud is obtained in a'well filterable state, If necessary, after filtering, the dyestufl may be freed from the 1.2 s aminonaphthol ethylproduct an aqueous solution of about grams of crystallized sodium sulfide.

ether-6-sulf0nic acid still present. The further diazotization is favorably carried out by an indirect method, as described above with regard to the aminoazodyestuff. The diazo compound is likewise isolated and finally coupled with a cold solution containing 350 grams of sodium bicarbonate, 363 grams of 1.8 acetylaminonaphthol 3.6 disulfonicacid, 10 liters of water and 5 liters of pyri is added tothe aqueous solution of the rereduction is finished at a temperature separating is dine. The dyestufi which separates by salt ing out is worked up in the usual manner and corresponds to the following formula.

COOH

HO3S- O-C2Ht CH3. CO. HN OH N It is a dark powder, dyeing cotton green shades of good fastness to light.

l SOsl-I CH3 Example 2 v 337 grams of the condensation product from p-phenylenediamine-mono-suli'onic acid and p-nitrobenzoylchloride are diazotized in the usual manner and coupled in a soda-alkaline or acid solution with 180 grams of acetoacetic-acid-anilide. When the coupling is complete, 420 grams of crystallized sodium sulfide are added. to the nitromonoazodyestuff, which, if necessary, has been dissolved by diluting. The reduction is finished quickly, and when the sulfur and the sulfur compounds have been removed there is further diazotized in an indirect manner as described in Example 1, and the isolated diazoazo compound is coupled with 267 grams of 1.2 amino-naphthol-ethyl-ether-6-sulionicacid. The aminodisazodyestuii thus obtained is isolated, and if necessary, freed from the amino-' naphtholethyl-ether-sulfonic acid by re-dissolving and again diazotized. Theyellowbrown diazodisazo-compound thus formed is filtered by suction and coupled with 363 grams of 1.8-acetylamino-naphthol-3.6-disul- C O l V the usual manner, having in its free state the following formula: V

on NH-CO-OH:

i O-CzH5 I Boas 803E SOKH is a bronze colored powder, dyeing cotton clear shades of good fastness properties, the shades being somewhat yellower than those of Example 1.

Similar dyestufis are obtained when replacing the 1.8-acetylaminonaphthol-3;6-disulfonic acid by another periacidyl aminonaphtholsulfonic acid, as for example, 1.8- bcnzoylaminonaphthol 4.6 disulfonic acid, 1.8-acetylaminonaphthol--sulfonic acid and the like.

E wample 3 The diazo compound from 337 grams of the condensation product of p-nitrobenzoylchloride and p-phenylenediamine-mono-sulfonic acid is coupled in a soda-alkaline solution with 180 grams of 8-methyl-l-phenyl-5- pyrazolone. The nitrogroup of the monoazodyestufi is reduced with Na s and, after indirect further diazotization of this aminoazodyestuff, the diazo compound thus formed is coupled with 267 grams of 1.2 aminonaphthol-ether-6-.sulfonic acid. When the coupling is complete, the aminodisazodyestuff, which, if necessary, is further purified, is again diazotized as described above, and finally coupled with 363 grams of 1.8-acetylamino-naphthol-3.6-disulfonic acid in the presence of sodium bicarbonate in pyridine. The dyestuff to be isolated in the usual manner and having in its free state the following and dyeingcotton green shades of good fast formula: ness to light.

/N=C. CH3 I l V I 5 OCHN=NONH. o 0 N (611) do n I? noas I -O. CzHs I '7 -OH3CO.HN on I noss SOaH dyes cotton green shades of good fastness to When employing instead of p-nitrobenzoyl light. chloride the m-nitrobenzoylchloride, cotton Ewmple 4 is dyed in a somewhat bluer shade. The diazo compound from 218 grams of 4:- I Claim! V 29 nitroaniline-iZ-sulfonic acid is combined in a 1. The azodyestufis of the probable gensoda-alkaline solution with 145 grams of salieral formula a OH NH.aG

cylic acid and the nitro group of this monowherein R stands for the radical of acouazodyestuif is reduced with an aqueous solupling component of the group consisting of tion of about 420 grams of crystallized phenols, salicylic acid compounds, aceto-acesodium sulfide at a temperature of about 40-60 C. The reduction is finished quickly, the aminoazo compound thus obtained is may be substituted by a sulfonic acid group, freed in the usual manner from sulfur and R stands for a benzene nucleus which may sulfur compounds and, after the addition of be substituted by halogen, alkyl or alkoxy. 106 grams of sodium carbonate at 'to 3R may be substituted by a sulf-onic acid C. it is slowly condensed with about 200 group, alk stands for an alkyl group, ac grams of p-nitrobenzoylchloride. The opstands for an acyl group and n stands for erations then following: reduction of the one of the numbers one and two, being in the nitro group, diazotization and coupling with form of their alkali metal salts dark powl.2-aminonaphtho1 ether 6 sulfonic acid, ders, dyeing the vegetable fibre green shades again diazotization and final coupling with of good fastness to light. 1.8-acetylaminonaphthol-3.6-disulfonic acid 2. The azodyestuffs of the probable genare performed as described in Example 1. eral formula: v

l-ones, R stands Oak SOaH In this manner there is obtained a dyest ufi; wherein R stands for c a benzene nucleus having in 1ts free state the following formula: group, R stands for a benzene nucleus which 55 a 1 I V V V M3? 1 c 0 on s 03H ac 0162a 0H3. CO.HN OH I HOsS tic acid arylamides, methylkctol and pyrazo for a benzene nucleus which which may be substituted by a sulfonic acid.

be substituted by halogen, alkyl or alkoxy, alk stands for an alkyl group, 210 stands for an acyl group and n stands for one of the numbers one and two, being in the form of their alkali metal salts dark powders, dyeing the vegetable fibre green shades of good fastn-ess to light.

3. The azodyestufis of the probable general formula:

wherein R stands for abenzenenucleuswhich may be substituted by a sulfonic acid group. R stands for a benzene nucleus which may be substituted by halogenyalkyl or alkoXy, alk stands for an alkyl group and ac stands for an acyl group, being in the form of their alkali metal salts dark powders, dyeing the vegetable fibre green shades of good fastness to light. 7

4. The azodyestufl' of the following formula:

O -alk OH IIIH-ac OaH Hogs

orn-oo-my on being a dark powder, dyeing cotton green shades of good fastness to light.

5. The az-odyestuff of the following mula:

430011 SOa'H N m N HOaS som being a dark powder and dyeing cotton green shades of good fastness to light.

In testimony whereof, I affix my signature.

EUGEN GLIETENBERG. 

